Insecticidal 1,3-benzodioxol derivatives

ABSTRACT

THE PRESENT INVENTION CONCERNS NOVEL COMPOUNDS OF THE FORMULA:   (R1(CH2)S-Y-C(-R4)(-R5)-(C(-R6)(-R7))V-(C(-R8)(-R9))W)R2C=   C(-R3)-(CH2)S-X-AR1   WHEREIN R1 TO R11 HAVE VARIOUS SIGNIFICANCES INCLUDING E.G. ALKYL, X AND Y INCLUDE O AND S AND S, V AND W ARE WHOLE NUMBERS AND AR1 IS PHENYL OR SUBSTITUTED PHEMYL, THE COMPOUNDS POSSES INSECTICIDAL PROPERTIES.

United States Patent US. Cl. 260340.5 24 Claims ABSTRACT OF THE DISCLOSURE The present invention concerns novel compounds of the formula:

wherein R to R have various significances including e.g. alkyl, X and Y include 0 and S and s, v and w are whole numbers and Ar is phenyl or substituted phenyl.

The compounds possess insecticidal properties.

The present invention relates to ethers and thioethers and more specifically to aromatic ethers and thioethers. The present invention provides compounds of formula I,

wherein AI, is

wherein W is alkyl of 1 to carbon atoms, fluorine, chlorine or bromine,

Z is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxy of 1 to 5 carbon atoms, alkenyloxy of 2 to 12 carbon atoms, formyl, alkyl carbonyl of 2 to 6 carbon atoms, alkoxy carbonyl of 2 to 6 carbon atoms, monoor di-alkyl substituted carbamoyl each alkyl substituent being of 1 to 5 carbon atoms, alkoxy methylene of 2 to 6 carbon atoms, alkylthio of 1 to 5 carbon atoms, fluorine, chlorine, bromine, cyano or nitro,

R and R which may be the same or different, are

each hydrogen or alkyl of l to 5 carbon atoms,

11 and p, which may be the same or different, are each q is 0 or 1,

misO, 1,2, 3 or 4,

R is alkyl of l to 11 carbon atoms, non-cyclic hydrocarbon of up to 11 carbon atoms having one or two double bonds or one triple bond, cycloalkyl of 4 to 7 carbon atoms, alkyl substituted cycloalkyl of 4 to 7 ring carbon atoms the alkyl substituent having 1 to 5 carbon atoms, cycloalkenyl of 4 to 7 carbon atoms, alkyl substituted cycloalkenyl of 4 to 7 ring carbon atoms the alkyl substituent having 1 to 5 carbon atoms, phenyl, Ar which has the same definition as -Ar above wherein Ar and Ar may be the same or different,

R R R R R R R and R which may be the same or different, are each hydrogen, alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 6 carbon atoms,

Y is oxygen or sulphur,

X is oxygen, sulphur, OCH ---or SCH s, v, and w, which may be the same or different, are

each 0, or 1, and

zis1,2or3. ,i.

!It is to be understood that the terms alkyl, alkenyl, alkoxy and non-cyclic hydrocarbon cover both; straight and branched chain configurations thereof. v

The present invention also provides a process for 'tlie production of a compound of formula I, which comprises (a) Reacting a compound of formula II,

3 -31 4 i wherein I a R1 R2 R3 R4: R5: R6, R7, R8, R9, Y, s, V, W Z

are as defined above, and Hal is chlorine or bromine,

with a compound of formula III,

MXAr III wherein Ar and X are as defined above, and

'M is hydrogen, potassium or sodium,

with the proviso that when M is hydrogen, thereactiohlis effected in the presence of an acid binding agent,

(b) Reacting a compound of formula IV,

[ t i-( ii wherein 2 3 4, 5, 6, 7, R R X, Ar v and w are as defined in relation to formula I,

Hal is chlorine or bromine, and

z is l,

with the proviso that v-I-w is 0 or 2 or when v+w is 1,

R and R or R and R are'other than hydrogen,

with an alcoholate or thioalcoholate of formula V, L

R (CH YMe mo=o om .XAr; 1 t,

Ra iv V wherein R ,Y and s are as defined in relation to formula I, and Me is sodium or potassium,

to produce a compound of formula Ia, i.e. a compound of formula I wherein z is l, v+w is 0 or 2, or when v+w,,;is

1, R and R or R and R are other than hydrogen (c) Condensing a compound of formula VIa,

Via

wherein R1 R2! R3, R4 R5, R6, R7 R8 R9: Y, w and Z are as defined in relation to formula I, with a compound of formula IIIa Ar 'OH IIIa wherein Ar, is as defined in relation to formula I, in the presence of dicyclohexylcarbodiimide as condensation agent, to produce a compound of formula Ib, i.e. a compound of formula I wherein X is oxygen, or

a 3 .(d) Reacting a compoundof formula VIa or Vib,

VIb

wherein R1 R2, R3! R4, R R6, R7, R3, R9, Y, S, V, W and Z are as defined in relation to formula I,

or an alkali alcoholate or thioalcoholate thereof respectively with a compound of formula VII,

with the proviso that when a compound of formula VIa or VIb is reacted in the free alcohol or thioalcohol form thereof respectively, the reaction is effected in the presence of an acid-binding agent, to produce a compound of for-' mula Ic i.e. a compound of formula I wherein X is --OCH or -SCH The production of compounds of formula I in accordance with process (a) may be effected as follows viz.

A compound of formula III is conveniently reacted in a solvent, for example, a hydrocarbon such as benzene, an ether such as dioxane, 1,2-dimethoxyethane, diethyleneglycol-dimethyl ether, an alcohol such as ethanol, tert. butanol, a ketone such as acetone, a nitrile such as acetonitrile, an acid amide such as dimethylformamide, or in an appropriate solvent mixture, in the presence of an acid binding agent, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium-tert.butoxide, at a temperature between prefer-. ably 0 and about 100 C. with a compound of formula II. Potassium iodide may, conveniently be added in catalytic amounts to the reaction mixture as catalyst.

When z of formula I is 2, reaction conditions which may cause a fi-elimination, e.g. the use of sodium or potassium hydroxide, in e.g. dimethylformamide as solvent, are avoided.

Working up of the reaction product is effected in the usual manner.

The production of compounds of formula Ia in accordance with process (b) may be effected as follows viz.

A compound of formula IV is reacted, conveniently in an appropriate reaction medium, for example an ether such as dioxane, 1,2-dimethoxyethane, diethyleneglycoldimethyl ether, a hydrocarbon such as benzene, or provided that Y in formula V signifies oxygen, in an alcohol of formula R (CH ),OH wherein R and s correspond to those of formula V, or provided that Y in formula V signifies sulphur, in a mercaptan of formula R (CH ,SH

- wherein R and s correspond to those of formula V, preferably at a temperature between room temperature and about 100 C., over a period, e.g. 3 to hours, with a compound of formula V. Working up of the reaction product is effected in the usual manner.

The production of compounds of formula Ib in accordance with process (c) may be effected as follows viz.

A compound of formula VIa or V'Ib is reacted, conveniently in an appropriate solvent, for example a hydrocarbon such as benzene, an ether such as 1,2-dimethoxyethane, an alcohol such as ethanol or tert.butanol, a ketone such as acetone, a nitrile such as acetonitrile, an acid amide such as dimethyl formamide, or in an appropriate solvent mixture, in the presence of an acid binding agent, for example sodium hydroxide and potassium hydroxide, at a temperature between and 100 C. with a compound of formula VlII. Working up of the reaction product is effect in conventional manner.

When the compounds of formula VIa and VIb are reatced in the form of an alkali alcoholate or thioalcoholate,

the reaction may be effected in the absence of an acid binding agent. The reaction may be effected in an appropriate solvent, such as benzene, tert.butanol, 1,2-dimethoxyethane, dimethylformamide. Working up is effected in the usual manner.

The compounds of formula I are generally colourless oils or crystalline and may be characterized in the usual manner.

The compounds of formula II employed as starting material in the production of compounds of formula I in accordance with process (a) above, may be produced by a process as follows viz.

(a) Reacting a compound of formula VIII,

wherein 1 2 3, 4, 5, 6, R R R Y, s, v, and w are as defined in relation to formula I,

VIII

with a halide transmitter e.g. hydrobromic acid, thionyl halides or a suitable phosphorous halide in the presence of an acid binding agent to obtain a compound of formula Ila i.e. a compound of formula II, wherein z is 1.

(b) Reacting a compound of formula XI,

4 R (CHg) -O-(J-Cl a XI wherein R R R and s are as defined in relation to formula I,

with a compound of formula XII,

R R XII wherein R R R and R ar eas defined in relation to formula I,

if required, in the presence of an appropriate catalyst, such as anhydrous zinc chloride, to produce a compound of formula I Ib i.e. a compound of formula II wherein Y is oxygen, Hal is chlorine, z and v are 1 and w is 0.

(c') Reacting a compound of formula VIa, wherein z is 3, with an appropriate halide transmitter e.g. hydrobromic acid, a thionylhalide or a suitable phosphorous halide in the presence of an acid binding agent, to produce a compound of formula IIc i.e. a compound of formula II, wherein z is 3.

(d') Reacting a compound of formula XIIIa,

wherein R R are as defined in relation to formula 1, Hal is chlorine or bromine, each of R R R R R and R is hydrogen, and each of v and w is 0 or 1, with a compound of formula V, to produce a compound of formula IId i.e. a compound of formula II, wherein R and R is hydrogen, and each of v and w is 0.

(e') Reacting a compound of formula XIV,

XIII

wherein 1 2- 3 4 5, 6, R7, R R Y, s, v, and w are as defined in relation to formula I,

with concentrated hydrochloric or hydrobromic acid, preferably of 48% by weight concentration, to produce a compound of formula IIe i.e. a compound of formula II, wherein z is 2 and Hal is chlorine or bromine.

The production of compounds of formula IIa in accordance with process (a) may be effected as follows viz.

The reaction temperature and solvent depend on the halide transmitter employed. Thus, with 48% by weight hydrogen bromide or hydrochloric acid no solvent is required and the reaction temperature may be between -20 and 0 C. With thionylhalides, a suitable solvent is ether and a suitable reaction temperature is room temperature. With phosphorous halides, e.g. phosphorous tribromide, pyridine may be employed as solvent which also serves as acid binding agent and a suitable reaction temperature is between 20 and 0 C.

The purification of the resulting compound of formula IIa may, if desired be omitted, and the compound may be employed directly in the production of compounds of formula I in accordance with process (a) above.

The compounds of formula XIII employed as starting material in process (a) above may, for example, be produced by reacting a compound of formula IX,

1 2, 4, 5, 6, R Y, v, and w are as defined in relation to formula I,

with a compound of formula X,

HzC=C wherein R is as defined above, and Mt is MgCl, MgBr or Li in organometallic bond,

in an appropriate solvent, such as tetrahydrofuran, and subsequent hydrolysis of the resulting magnesium or lithium compound in the usual manner.

The compounds of formulae IX and X employed in the production of compounds of formula VIII above are known or may be produced in accordance with known methods.

The production of compounds of formula 11b in accordance with process (b) may be effected as follows viz.

The reaction may be effected with or without a solvent. An example of a suitable solvent is ether. The reaction temperature may vary between 0 and 30 C.

The starting compounds of formulas XI and XII employed in process (b) above are either known or may be produced in accordance with known methods.

The production of compounds of formula IIc in accordance with process (c') above may be effected as follows The reaction conditions will vary with the actual halide transmitter employed. Thus, with 48% by weight hydrogen bromide no solvent is required and a suitable reaction temperature is between 20 and 0 C. With thionylhalides a suitable solvent is ether or benzene and a suitable reaction temperature is between and 25 C. With phosphorous halides e.g. phosphorous tribromide, a suitable solvent and acid binding agent is pyridine the reaction temperature varying between -20 C. and room temperature.

The starting compounds of formula VIa, wherein z is 3 employed in process (c') and also in process (c) above for the production of some of the compound of formula Ib and in process (d) above for the production, of some of the compounds of formula Ic, may be produced by sodium bromohydride reduction of a compound of formula XVI,

wherein R1, R2, R3, R4, R5, R5, R7, R8, R9, Y, S, V and ware 8S defined in relation to formula I, and z is 3, I

in manner known per se.

The compounds of formula XVI, may, for example, be obtained by reacting the compounds of formula VIII with alkyl vinyl ethers in the presence of mercury-II- acetate at an elevated temperature, preferably for a period of e.g. 4 days, and subsequent transposition by short heating to l60l90 C., preferably over 1 to 2 hours.

The production of compounds of formula IId in accordance with process (d') may be effected as follows viz. The compounds of formulae V and XIIIa are dissolved in a suitable solvent e.g. an alcohol of formula R (CH OH- or thioalcohol of formula R (CH ,SH wherein R and s correspond to those of formula V, and acid amide e.g. dimethyl formamide, or a sulphoxide e.g. dimethyl sulphoxide and the reaction is effected at a temperature of between 0 and C. preferably between 20 and 30 C. t

The starting compounds of formula XIIIa employed in process (d') above are either known or may be produced in accordance with known methods.

The production of compounds of formula He in accordance with process (e) may be effected as follows; I

The compound of formula XIV and either 48% by weight hydrogen bromide or concentrated hydrochloric acid are reacted at a temperature of about 0 C. A solvent is not required.

The compounds of formula XIV employed as starting material in process (e') above may be produced by reacting a compound of formula 1X with a Grignard compound of formula XV,

v wherein R is as defined in relation to formula I,

and subsequent hydrolysis of the magnesium compound.

The compounds of formula III employed as a starting material in process (a) above for the production of compounds of formula I, are known.

The compounds of formula IV, employed as a starting material in process (b) above for the production of compounds of formula Ia may be produced by reacting a compound of formula XIII,

wherein XIII The compounds of formula VIa employed as a starting material in processes (b) and ((1) above for the production of compounds Ib and 10 respectively, when z is 3 has already been described. The production of compounds of formula VIa when 2 is 1 or 3 may be effected by reacting a compound of formula II, wherein z is 1 or 3, with aqueous alkali e.g. potassium hydroxide in manner known per se.

The compounds of formula VIa when z is 2 may be effected by reacting a compound of formula II wherein z is 2 with potassium acetate, preferably in glacial acetic acid under reflux and hydrolysing the resulting acetate with methanolic potassium hydroxide.

The compound of formula VIb employed as a starting material in process (d) above for the production of some of the compounds of formula 10, wherein z is 1 or 3 may be produced as follows viz.

Reacting a compound of formula II, wherein z is l or 3 with thiourea or ammonium dithiocarbamate in water at about 100 C. and subsequent alkaline hydrolysis of the resulting compound with e.g. 5N potassium hydroxide.

,The compounds of formula VIb, wherein z is 2 may, for example, be produced by reacting a compound of formula II, wherein z is 2 with an alkali thioacetate e.g. potassium thioacetate, in e.g. dimethyl sulphoxide or acetonitrile, as solvent followed by alkaline hydrolysis e.g. with methanolic potassium hydroxide.

The compounds of formula I are useful because they exhibit 'an inhibiting effect on the development of the insects.

Dysdercus fasciatus (Egyptain cotton worm) Prodenia littura (cotton stainer) Tenebrio molitor (flour beetle) and Tetranychus urticae (red spider) from one development stage thereof to the next, to result either in death or reduced oviposition or inhibition of copulation as indicated by the following tests viz.

TEST 1 Insecticidal effect on Dysdercus fasciatus larvae (Egyptian cotton worm) Filter paper is impregnated with a solution of a c0m pound of formula I. A box made from polystyrene (200 x x 85 mm.) is coated with the filter paper treated in this way. A folded filter paper which is also impregnated and covered with about 30 Dysdercus larvae of the 4th larval stage is placed into this box. Pounded cotton seeds as food and a drinking-vessel are placed into it. The number of adults which have developed normally after 14 to 15 days is determined.

TEST 2 Effect on the development of Prodenia littura larvae (cotton stainer) into adults Filter paper is impregnated with a solution of a compound of formula I. Partitions, having a size of 3.5 x 5.5 cm., of a plastic box are coated with the filter paper treated in this way. One Prodenia caterpillar in the third to fourth larval stage is placed into each partition and a piece of artificial medium is given as food. The insects are kept at The number of the adults which have developed normally after 21 days is determined.

TEST 3 Effect on the development of Tenebrio molitor chrysales (flour beetle) into adults A compound of formula I is used at a concentration of 1% by weight in acetonic solution. 2 ,ul. of the resulting solution, corresponding to 20 micrograms of compound,

are applied on the abdominal side of the last three segments of young chrysales (not older than 18 hours) by means of a l-microlitre bulb pipette. 10 chrysales are used for each test. The treated chrysales are kept at 28 in plastic cups. The adults which have developed normally are counted after 10 to 12 days.

TEST 4 Contact effect in T etranychus urticae (red spider) One day before treatment 10 adult females of Tetranychus urticae are placed by means of a pencil between two rings (diameter: 3 cm.) of caterpillar lime which are applied to a leaf of a cotton plant. The cotton leaves are sprayed to run otf by means of a sprayer with a liquor containing 0.1% by weight of a compound of formula I. After drying, the plants are kept at room temperature and in light. The dead and live insects are counted 6 days after the treatment. The relation between the treated and one untreated population shows the effect.

From LD oral or dermal determinations on the male rat, a low toxicity of the compounds of formula I towards warm blooded animals is indicated.

For the above-mentioned use, the amount applied to a locus to be treated e.g. a plant culture, will of course vary depending on the compound employed, the mode of application, ambient conditions, and the insects to be combated. However, in general satisfactory results are obtained when a compound of formula I is applied to the locus in an amount between 1 and 10 kg./hectare, the application being repeated as required.

The compounds may be applied to the locus with conventional applicator equipment and by conventional methods e.g. strewing, spraying and dusting.

Compositions may be produced in conventional manner and may comprise a compound of formula I in ad mixture with insecticidal carriers e.g. talc, diatomaceous earth, bentonite and pumice, insecticidal diluents e.g. Water or appropriate organic solvents such as alcohols, petroleum and tar distillates and/ or insecticidal adjuvants e.g. emulsifying agents, solvent aids such as mineral oils and wetting and adhesive agents such as cellulose derivatives.

Concentrate forms of the compositions may generally contain between 2 and preferably between 5 and 50% by weight, of a compound of formula I.

Application forms of the composition may generally contain between 0.01 and 0.1%, by weight of a compound of formula I.

Preferred compounds of formula I are as follows:

5- 5-tert.butoxy-3-methyl-2-pentenyloxy 1,3-benzodioxol,

5 5 -isopropylthio-3-methyl-2-pentenyloxy 1,3-benzodioxol,

4- 3-ethyl-5-sec.butoxy-2-pentenloxy) benzoic methyl ester,

4'- 3-ethyl-5-sec.butoxy-2-pentenyloxy) -acetophenone,

5 5 -cyclopentyloxy-3 -methyl-2-pentenyloxy 1,3-benzodioxol,

5 3-methyl-5 Z-pentyloxy) -2-pentenyloxy] 1,3-benzodioxol,

5 (5-isopropoxy-3-metl1yl-2-pentenyloxy)-methyl]- 1,3-benzodioxol,

5 5 -isopropoxy-3-methyl-2-pentenyloxy 1,3-benzodioxol,

4- (5 -isopropoxy-3 -methyl-2-pentenylthio chlorobenzene,

4- (5 -isopropoxy-3 -methyl-2-pentenyloxy thioanisole,

4- 5-isopropoxy-3-methyl-2-pentenyloxy) ethylbenzene,

5 5 -ethoxy-3-methyl-2-pentenyloxy) l ,S-benzodioxoal,

4- 6-ethoxy-3-methyl-2-hexenyloxy benzoic acid methyl ester,

4'- 6-ethoxy-3 -methyl-2-hexenyloxy -acetophenone,

5 -(4-isobutoxy-2-methyl-2-butenyloxy 1,3-benzodioxol,

5- 6-isopropoxy-4-methyl-3-hexenyloxy 1,3 -benzodioxo1.

'9 The following Examples illustrate the production of the compounds of formula I, but in no way limit the invention. The temperatures are indicated in degrees Centigrade. Where concentration is indicated as a percent, this is percent by weight.

EXAMPLE 1 2-(3-Ethyl-5-sec.butoxy-2-pentenyloxy)-benzaldehyde (according to process (a)) 10 1-bromo-3-ethyl-5-sec;butoxy-2-pentene is added without purification to 6.1 g. (0.05 mol) of salicylic aldehyde and 2.8 g. (0.05 mol) of potassium hydroxide in 80 cc. of 1,2-dimethoxy ethane. The mixture is stirred. at for 24 hours, 'is subsequently filtered and concentrated by evaporationat reduced pressure The residue is taken up in ether, extracted with icy cold 10% sodium hydroxide solution and subsequently with saturated salt solution, is dried wvith sodiumsulphate and evaporated.

The obtained 2-(3 ethyl-5-sec.butoxy -i2 pentenyloxy)- benzaldehyde may be purified by chromatography on silica gel with hexane/ethyl acetate l:1 as elant. {1 1.5090.

Analysis: C H O (molecular weight: 290.4). Calc.: C, 74.4%; H, 9.0%.-.Found: C, 74.1%; H, 9.2%.

In analogous manner as describedinBxample 1 but using the starting compound of formula VIII,v indicated in the following Table, the following compounds of general formula I are obtained.

Starting Analysis percent, compound or calm/found "formula III Empirical Molecular 7 produced in Example formula weight n 20 C v H 8 example N o.

2 2-(3-ethy1-5-isopropoxy-2-penteuyloxy)benzaldehyde 011E240: 276.4 1.5194 8.2; 64

3 4-(3-ethyl-5-isopropoxy-2-pentenyloxy)benzaldehyde 011E140: 276.4 1.5290 64 4 5-(3-ethyl-5-sec-butoxy-2-pentenyloxy-l,3-benzodioxol..-.;. 0 3111.0 306.4 1.5104 66 5 5-(3-ethy1-5-isopropoxy-2-penteny1oxy)-1,3-benzodioxol 0 E1 0; 292.4 1.5128 23.3 64

6 5-(5-tert-butoxy-3-methy1-2-pentenyloxy)-1,3-benzodioxo1 011112404 292.4 1.5124 67 7 5-(5-isopropylthlo-3-methyl-Z-pentenyloxy)-1,3-benzodioxol.. CIIHHOIS 294.4 1.5481 68 8. 5-(fi-cyclohexyloxy-B-methyl-2-penteny1oxy)-1,3-benzodloxo1 CnHnOr 318.4 1.5310 70 9... 4-(3ethyl-5-sec.butoxy-2-pentenyloxy)benzoic methyl ester. CiaH2a04 320-4 -511 66 10 4-(3-ethyl-5-isopropoxy-2-pentenyloxy)benzoic methyl ester iaHz|0| 306-4 1 1 5 64 11 4-(5-tert.butoxy-3-methyl-2-pentenyloxy)benzoie methyl ester- CIBH2I04 .4 1 514 67 12 4-(5-isopropylthio3-methy1-2-pentenyloxy)benzoic methyl 0111124033 308.4 1.5461 66. 2 7.8 10. 4- ester. 66. 1 8. 1 10. 5

13 4'-(3-ethyl-5-see.butoxy-2-pentenyloxy)acetophenone 019E280! 304-4 1-5214 14 4-(S-eyelohexyloxy-3-methyl-2-pentenyloxy)-benzoicacid- C2oH2aO4 332.4 1.5299 72.3 8.5

methylester. 72. 7 8. 8

15 4'-(3-ethyl-5-see.butoxy-2-pentenyloxy)-butyrophen0ne n nOa 332-5 1-5154 66 16 4-(3-ethy1-5-see.butoxy-2-pentenyloxy)-benzoicacid-isopropy1- 21112104 348.5 1.5037 72.4 9.3 66

ester. 72.6 9. 5

17.. 5-(5-cycl0pentyloxy-3-methyI-Z-pentenyloxy)-1,3-benzodioxol C1a nO4 304.4 1.5301

18 5-[Ii-methyl-5-(3pentyloxy)-2-penteny1oxy]-1,3-benzodloxol txHau04 306-4 1-5118 73 19 5-l3-methy1-5-(Z-pentyloxy)-2-penteuy1oxy1-1,3-benzodioxol 019112004 306.4 1.5080 2 20 5-(5-ethoxymethyl-2-penteny1oxy)-1,3benzodioxol (315E200; 264.3 1. 5240 21 5-(5-n.butoxy-3-methyl-2-pentenyloxy)-1,3-benzodioxo1 011112404 29 -4 1.5142 23-4 v 74 22 5-[ii-mathyl-5-(G-methyI-Bhepten-Z-yloxy)-2-penteny1oxy]-1,3- 011113004 346.5 1.5160 72.8 8.7 77 I benzodioxol. 73.0 9.0

23'. 4'-(5-etl1oxy-3,5-dimethyl-Z-hexenyloxy)-acetophenone (JiaHzaoa 29 .4 1- gig 3 3 7G EXAMPLE 24 -(5-Isopropoxy-3-rnethy1-2-pentenyloxy)-1,3-benzodioxol (according to process (a)) 1.7 g. (0.03 mol) of pulverised potassium hydroxide are added to a solution of 4.1 g. (0.03 mol) of 3,4-methylendi- 'oxy-phenol and 6.2 g. (0.035 mol) of l-chloro-S-isopropoxy-3-methyl-2-pentene in 100 cc. of 1,2-dimethoxyethane. The mixture is stirred at 60 for a period of 18 hours, is subsequently-filtered and evaporated at reduced pressure. The residue is dissolved in ether, washed with 5% solution of sodium hydroxide and subsequently with saturated salt solution, dried with sodium sulphate and evaporated.

The remaining 5-(S-isopropoxy-3-methyl-2-pentenyloxy)-1,3-benzodioxol is purified by chromatography on silica gel with hexane/ethyl acetate 9:1. A chromatographically uniform and colourless oil is obtained which according to gas-chromatogramme and NMR-spectrum consists of a mixture of of the 2-cis and 70% of the Z-trans compound. n -=1.5167.

Analysis: C H O (molecular weight: 278.3). Calc.: C, 69.0%; H, 7.9%. Found: C, 68.5%; H, 7.9%.

In analogous manner as described in Example 24, but using the starting compounds of formula III indicated in the following Table, the following compounds of general formula I are obtained:

7 Empirical Molecular 4'-(6-Ethoxy-3-methyl-2-hexenyloxy)-acetophenone n =1.5266. p Analysis: C H- O (molecular weight: 276.4). Calc.: C, 73.9%; H, 8.8%. Found: C, 73.5%; H, 8.8%.

EXAMPLE 36 5 (4-Isobutoxy-2-methyl-2-butenyloxy)-1,3-benzodioxol (according to process (a)) 2.21 g. (0.01 mol) of 1-bromo-4-isobutoxy-Z-methyl-Z- butene are added at 0 during the course of 5 minutes to 1.38 g. (0.01 mol) of 3,4-methylendioxy-phenol and 0.56 g. (0.01 mol) of potassium hydroxide in cc. of 1,2-dimethoxyethane. After stirring the reaction mixture at room temperature for 24 hours it is filtered and the solvent is distilled off at reduced pressure. The residue is dissolved in ether, Washed with saturated salt solution, dried with sodium sulphate and evaporated. The residue is purified by chromatography on silica gel with hexane/ ethyl acetate 9: 1. 5- (4-isopropoxy-2-methyl-2-butenyloxy)-1,3-benzodioxol is obtained as colourless oil. n =1.5 150.

Analysis percent gale/found l Starting compound 5-(6-Ethoxy-3-methyl-2-hexeny1oxy)-1,3-benzodioxol (according to process (a)) hexane/ethyl acetate 9: 1, 5-(6-ethoxy-3-methyl-2-hexenyloxy)-1,3-benzodioxol is obtained as colourless oil. n =1.5192.

Analysis: C H O (molecular weight: 278.3). Calc.: C, 69.0%; H, 8.0% Found: C, 68.9%; H, 8.1%.

In analogous manner as described in Example 33, but using 4-hydroxy-benzoic acid-methyl ester in the place of 3,4-methylendioxyphenol, the following compound of general formula I is produced: 1

EXAMPLE 34 4-(6-Ethoxy-3-methyl-2-hexenyloxy)-benzoic methyl .ester', n =1.52O2. Analysis: C H 0 (molecular weight: 292.4). Calc.: C, 69.8%.; H, 8.3%..E0'u C, 69.5%; H...8-. v

Example formula weight C H Br 01 N S of formula III 25 2-(5-isopropoxy3-methy1 2-pentenylthio)- 0171121038 308.4 1.5492 66.2 7.8 10.4 2-mercaptobenzoicbenzoicacid-methylester. 66.9 7.9 10.4 acid-methylester.

2e 3-(5-isopropoxy-3-methyl-2-pentenyloxy)- CrsHnBlOa 313.2 1. 5138 57.5 6.8 25.5 3-brornopheno1.

bromobenzol. 58. 1 7. 0 25. 1

27 4-(5-isopropoxy-3-methyl-2-pentenylthio)- C15H OlOS 284.8 1.5332 63.3 7.4 12.4 11 3 4-chlorophenol.

chlorobenzol. 63. 1 7. 6 13.0 10 6 28 4-(5-isopropoxy-3-methyl-2-pentenyloxy)- CmHMOa 264.4 1.5050 72.7 9.2 4-methoxyphenol.

anisole. 72. 3 9. 5

29 4-(5-is0propoxy-3-methyl-2-pentenyloxy)- CMHMOZS 280.4 1.5329 68.5 8.6 4-(methylthio)- thioanisole. 68. 0 8. 6 phenol.

30 4-(5-isopropoxy-3-methyl-2-pentenyloxy)- CuHzuOz 26 .4 1- 4992 77.8 10.0 4-ethylphenol.

ethylbenzol. 77. 5 10. 7

31 4-(5-isopropoxy-B-metl1yl-2-pentenyloxy)- C15H1N04 279.3 1.5335 64.5 7.6 5.0 4-nitrophen0l.

nitrobenzol. 64. 4 7. 7 4. 8

32 4-(5-isopropoxy-3-methyl-2-pe11teny1oxy)- C15H20Cl20z 303.2 1.5244 59.4 6.6 23.4 2,4-dichlorophenol.

1,3-dichlorobenzol. 59.4 6.6 23.6

EXAMPLE 33 Analysis: C H O (molecular weight: 278.3). Calc.:

C, 69.0%; H, 8.0%. Found: C, 69.0%; H, 8.3%.

EXAMPLE 37 5-(6-Isopropoxy-4-methyl-3-hexenyloxy)-1,3-benzodioxol (according to process (a)) 2.35 g. (0.017 mol) of potassium carbonate and 50 mg. of potassium iodide are added to a solution of 4.0 g. (0.017 mol) of 1-bromo-6-isopropoxy-4-methyl-3-hexene and 2.35 g. (0.017 mol) of 3,4-methylendioxy-phenol in 120 cc. of acetone. The suspension is boiled under reflux during the course of 20 hours, is then filtered and liberated from acetone in a vacuum. The residue is taken up in ether, washed with water and saturated salt solution, dried over sodium sulphate and evaporated. The residue is chromatographed on silica gel with hexane/ethyl acetate 9: 1. Thus the cis/trans isomeric mixture of the 5-(6-isopropoxy-4-methylmethyl-3-hexenyloxy) 1,3 benzodioxol is obtained as colourless oil. r1 1.5111.

Analysis: C17H2404 (molecular weight: 292.4). Calc.: C, 69.8%; H, 8.3%; O, 21.9%. Found: C, 68.9%; H, 8.5%; O, 22.7%. I I

' EXAMPLE 38 4-(S-Isopropoxy-2-pentenyloxy)-aeetophenone (according to process (a)) 3.4 g. (0.06 mol) of pulverised potassium hydroxide are added to a solution of 8.2 g. (0.06 mol) of p-hydroxy- 699192991 91 1 455 3- (009 1 9 h .r9- op poxy-2-pentene in 100 cc. of 1,2-dimethoxyethane. The mixture is stirred at 60 during the course of 24 hours and is subsequently filtered. The filtrate is evaporated at reduced pressure, the residue is taken up in ether, and the ether solution is washed with saturated salt solution. The organic phase is dried with sodium sulphate and evaporated. The residue is chromatographed with hexane/ ethyl acetate 4:1 on silica gel and then the 4-(5-isopropoxy-2- pentenyloxy)-acetophenone is obtained as colourless oil. 11 1.5240.

Analysis: C16H22O3 (molecular weight: 262.3). Calc.: C, 73.3%; H, 8.5%; O, 18.3%. Found: C, 73.3%; H, 8.6%; O, 18.2%.

In analogous manner as described in Example 38, but using 3,4-methylendioxy-phenol in the place of p-hydroxyacetophenone, the following compound of general formula I is produced:

EXAMPLE 39 5 (5 -Isoprop oxy-2-pentenyloxy) 1,3 -benzodioxol Analysis: C H O (molecular weight: 264.3). Calc.: C, 68.2%; H, 7.6%; O, 24.2%. Found: C, 68.4%; 8.0%; O, 24.1%.

EXAMPLE 40 4- 5-Isopropoxy-2-pentenylthio -methyl] -chorobenzol (according to process (a)) 8.1 g. (0.05 mol) of 1-chloro-5-isopropoxy-2-pentene are added dropwise at 20-25 during the course of 10 minutes and while stirring to a solution of 7.9 g. (0.05 mol) of 4-chloro-benzylmercaptan and 5.6 g. (0.05 mol) of potassium tert.butoxide in 150 cc. of tert.butanol. The solution which is rendered turbid during the addition is stirred at 60 during the course of 1 hour and is then cooled and filtered. The solvent is distilled off at a reduced pressure, the residue is dissolved in ether and the ether solution is washed with saturated salt solution. The ether phase is dried with sodium sulphate and then the ether is distilled ofr' and the residue is chromatographed on silica gel with chloroform. The 4-[(5-isopropoxy-Z-pentenylthio)-methyl]-chlorbenzol is obtained as colourless oil having a B.P. of 110-112/5.10 mm. n. =1.5391.

Analysis: C H ClOS (molecular weight: 284.8). Calc.: C, 63.3%; H, 7.4%; Cl, 12.4%; S, 11.3%. Found: C, 63.2%; H, 7.4%; Cl, 12.7%; S, 11.5%.

EXAMPLE 41 (5-Isopropoxy-3-methyl-2-pentenyloxy)-methyl] 1,3- benzodioxol (according to process (a)) 15.8 g. (0.1 mol) of 5-isopropoxy-3-methyl-1-penten-3- 01 are added dropwise at 5 during the course of 15 minutes and while stirring to 40 cc. of 48% hydrobromic acid. After 30 minutes at 0-5 the mixture is extracted with ether, the ether extract is extracted with soda solution and subsequently with saturated salt solution, is

dried with sodium sulphate and evaporated.

The obtained 1-bromo-5-isopropoxy-5-methyl-2-pentene (19.0 g.) is added to 17.4 g. (0.1 mol) of sodium salt of 3,4-methylendioxy-benzyl alcohol in 150 cc. of dimethylformamide and the mixture is stirred at 60 for 5 hours. The reaction mixture is poured on 300 cc. of water and extracted with ether. The ether solution is washed with water, dried with sodium sulphate and evaporated. The residue is chromatographed on silica gel with hexane/ ethyl acetate 9: 1. A mixture of cis and trans-5-[(5-isopropoxy- 3-methyl-2-pentenyloxy)-rnethyl]-1,3-benzodioxol is obtained as colourless oil. n =1.5088.

Analysis: C H Q; (molecular weight: 292.4). Calc.: C, 69.8; H, 8.3%. Found: C, 69.4%; H, 8.2%.

In analogous manner as described in Example 41, but using 5-ethoxy-3,5-dimethyl-1-hexen-3-ol in the place of 5-isopropoxy-3-methyl-1-penten-3-ol, the following compound of general formula I is produced.

5- (5-Ethoxy-3,S-dimethyI-Z-hexenyloxy) -methyl] 1,3-benzodioxol n =1.5038. Analysis: C H O (molecular weight: 306.4). Calc.: C, 70.6%; H, 8.6%. Found: C,.70.'6%; H, 9.2%.

EXAMPLE 43 5-[ 5-Isopropoxy-3-methyl-2-pentenyloxy -methyl] 1,3-benzodioxol (according to process (a)) 8.0 g. (0.2 mol) of sodium hydroxide are added to' a solution of 30.4 g. (0.2 mol) of3,4-methylendioxy-benzylalcohol in 300 cc. of benzene. The mixture is heated while stirring vigorously and kept at reflux temperature Whereby the water condensing in a refrigerator is separated by means of a water separator. After 24 hours 35.3 g. (0.2 mol) of 1-chloro-'5-isopropoxy-3-methyl-2-pentene are added dropwise during the course of 1 hour and the mixture is stirred underreflux for a further 16 hours.

The reaction mixture is cooled andthen washed with saturated salt solution, the benzene solution is dried with sodium sulphate, is dried and evaporated. The residue is fractionated at 10* mm. whereby the cis/trans mixture of 5 [(5 isopropoxy 3 methyl 2 pentenyloxy)- methyl] 1,3-benzodioxol distills at 126-136.

The product is identical with the compound produced in accordance with Example 41.

EXAMPIJE 44- 5-(4-Isobutoxy-3-methyl-2-butenyloxy) 1,3- benzodioxol (according to process (b)) 1.6 g. (0.01 65 mol) of sodium-isobutylate in 75 cc; 01' isobutanol are added dropwise at 70 during the course of 15 minutes to 4.3 g. (0.015 mol) of 5-(4-bromo-3- methyl-2-butenyloxy)-1,3-benzodi0xol which is dissolved in 130 cc. of isobutanol. After 3 hours at this temperature the reaction mixture is filtered, the solvent is distilled 01f at reduced pressure and the residue is dissolved in ether. The ether solution is washed with saturated salt solution, is dried with sodium sulphate and evaporated. The residue is chromatographed on silica gel with chloroform. 5 (4 isobutoxy 3 methyl-2-butenyloxy)-1,3- benzodioxol is obtained as colourless oil. n =1.5158.

Analysis: C H O (molecular weight: 278.3). Calc.: C, 69.0%; H, 8.0%; O, 23.0%. 'Found: C, 68.3%; H, 7.8%;0, 23.5.

In analogous manner as described in Example 44, but using 11. butanol as solvent and sodium-n. butylate in the place of sodium-isobutylate, the following compound of general formula I is produced:

EXAMPLE 45 5-(4-n.butoxy-3-methyl-2-butenyloxy-1,3-benzodioxol Analysis: C H O (molecular weight: 278.3). Calc.: C, 69.0%; H, 8.0%; O, 23.0%. Found: C, 68.6%; H, 8.2%; O, 22.8%.

In analogous manner as described in Example 44, but using 4' -(4-bromo-3-methyl-2-butenyloxy)-acetophenone in the place of 5-(4-bromo-3-methyl-2-butenyloxy)-1',3- benzodioxol, the following compound of general formula I is porduced:

EXAMPLE 46 4'-(4-Isobutoxy-3-methyl-2-butenyloxy)-acetophenone Analysis: C H O (molecular weight: 276.4). Calc.: C, 73.8%; H, 8.7%; O, 17.3%. Found: C, 73.4%; H, 9.1%; O, 18.1%.

"In analogous manner as described in Example 46, but using the sodium salt of the allyl alcohol and allyl alco- 15 hol as solvent, the following compound of general formula I is produced.

EXAMPLE 47 4- (4-Allyloxy-3-methyl-2-butenyloxy)-acetophenone EXAMPLE 48 [(4-Isobutoxy-3-rnethyl-2-butenyloxy -methyl] 1,3-benzedioxol n =l.5l02.

Analysis: C H OJ, (molecular weight: 292.4). Calc.:

C, 69.8%; H, 8.3%. Found: C, 69.4%; H, 8.1%.

EXAMPLE 49 4'-(4-Benzylthio-3-methyl-2-butenyloxy)-acetophenone (according to process (b)) 14.15 g. (0.05 mol) of 4'-(4-bromo-3-methyl-2-butenyloxy)-acetophenone are added at -15 during the course of 1 hour to 7.3 g. (0.05 mol) of sodium salt of benzylmercaptan which is dissolved in 120 cc. of dimethylformamide. The mixture is stirred at -25" for 20 hours, is subsequently filtered and the filtrate is evaporated at reduced pressure. The residue is dissolved in ether, is extracted with saturated salt solution and the ether solution is evaporated. The remaining yellowish oil is chromatographed on silica gel with hexane/ethyl acetate 2: 1. After recrystallization from ether/hexane the 4'-(4-benzylthio-3-methyl-2-butenyloxy)-acetophenone is obtained as colourless crystals. M.P. 7 5-76.5

Analysis: C H 0 S (molecular weight: 326.5). Calc.: C, 73.6%;H, 6.8%; S, 9.8%. Found: C, 73.3%;H, 6.7%; S, 9.7%.

EXAMPLE 50' 5- (4-Isobutylthio-3-methyl-2-butenyloxy) 1,3-benzodioxol (according to process (b) A solution of 4.3 g. (0.015 mol) of 5-(4-bromo-3- methyl-2-butenyloxy)-1,3-benzodioxol in 50 cc. of benzene is added at to 1.7 g. (0.015 mol) of sodium-isobutylthio alcoholate in cc. of benzene. The mixture is kept at reflux temperature for 13 hours, is subsequently filtered, washed with saturated salt solution and evaporated. The remaining yellow oil is chromatographed with hexane/ ethyl acetate 7 :1 on silica gel, whereby colourless 5-(4 isobutylthio 3 methyl-Z-butenyloxy)-1,3-benzodioxol is obtained. n =1.5463.

Analysis: C H O S (molecular weight: 294.4). Calc.: C, 65.3%; H, 7.5%; S, 10.9%. Found: C, 65.1%; H, 7.6%; S, 10.6%.

In analogous manner as described in Example 50 the following compound of general formula I is produced, whereby in the place of 5-(4-bromo-3-methyl-2-butenyloxy)-1,3-benzodioxol 4-(4-bromo 3 methyl-2-butenyloxy) -benzoic methyl ester is used.

EXAMPLE 51 4-(4-Isobutylthio-3-methyl-2-butenyloxy)-benzoic methyl ester n =1.5428. Analysis: C H O S (molecular weight: 308.4). Calc.: C, 66.2%; H, 7.8%; S, 10.4%. Found: C, 65.2%; H, 7.8%; S, 9.8%,

1-6 EXAMPLE s2 4-(4-Isobutoxy-3-methyl-2-butenyloxy)-benzoic methyl ester (according to process (b)) A solution of 6.0 (0.02 mol) of 4-(4-bromo-3-rnethyl-2- butenyloxy)-benzoic methyl ester and 2.9 g. (0.03 mol) of sodium-isobutylate in 130 g. of isobutanol is stirred at 70 for 6 hours. After this period the reaction mixture is filtered, the filtrate is evaporated at reduced pressure. The residue is dissolved in ether, the ether solution is washed with saturated salt solution, dried with sodium sulphate and evaporated. The residue (6.5 g.) is dissolved in 50 cc. of absolute methanol, 0.54 g. (0.01) mol of sodium methylate is added and the mixture is boiled under reflux for 2 hours. After this period 40 cc. of methanol are distilled off. The remaining residue is dissolved in cc. of ether, the ether solution is extracted twice with 100 cc. amounts of saturated salt solution and dried with sodium sulphate. The ether is distilled 01f and the resulting 4-(4-isobutoxy- 3-methyl-2-butenyloxy)-benzoic methyl ester is purified by chromatography on silica gel with hexane/ethyl acetate 20:1. n =1.5151.

Analysis: C H O (molecular weight: 292.4). Calc.: C, 69.8%; H, 8.3%; O, 21.9%. Found: C, 70.0%; H, 8.4%; O, 22.1%.

EXAMPLE 53 5 (4-Is obutoxy-2-butenyloxy -1,3-benzodioxol (according to process (b)) 1.9 g. (0.02 mol) of sodium-isobutylate in 30 cc. of isobutanol are added dropwise at 50 during the course of 2 hours to a solution of 5.4 g. (0.02 mol) of 5-(4-bromo-2- butenyloxy)-1,3-benzodioxol in 100 cc. of isobutanol. After stirring the reaction mixture at 50 for 6 hours it is filtered and the solvent of the filtrate is distilled olf at reduced pressure. The remaining oil is dissolved in ether, the ether solution is extracted with water, dried with sodium sulphate and evaporated. The residue is chromatographed with hexane/ ethyl acetate 12:1 on silica gel, whereby the 5-(4-isobutoxy-2-butenyloxy)-1,3-benzodioxol is obtained as colourless oil. n =1.5l02.

Analysis: C H O (molecular weight: 264.3). Calc.: C, 68.2%; H, 7.6%. Found: C, 67.4%; H, 7.5%.

The following compound is produced in manner analogous to that described in Example 53, but using 4- (4-bromo-2-butenyloxy)-acetophenone in the place of 5- (4-bromo-2-butenyloxy) -1,3-benzodioxol.

EXAIVHLE 54 4-(4-Isobutoxy-2-butenyloxy)-acetophenone Analysis: C H O (molecular weight: 262.3). Calc.: C, 73.3%; H, 8.5%. Found: C, 73.5%; H, 8.6%.

In manner analogous to that described in Example 53 the following compound is produced, whereby 5-[(4- bromo-2-butenyloxy)-methyl]-1,3-benzodioxol is used in the place of 5-(4-bromo-2-butenyloxy)-1,3-benzodioxol:

EXAMPLE 5 5 5- 4-Isobutoxy-2-buteny1oxy) -methyl] -1,3-

benzodioxol n =1.5110. Analysis: G T-1 0 (molecular weight: 278.3). Calc.: C, 69.0%; H, 8.0%. Found: C, 68.7%; H, 7.9%.

EXAMPLE 56 5 (7-Isopropoxy-5 -methyl-4-heptenyloxy -1, 3- benzodioxol (according to process (0)) A mixture of 2.5 g. (0.013 mol) of 7-isopropoxy-5- methyl-4-cis,trans-heptenol, 1.25 g. (0.009 mol) of 3,4

methylendioxy-phenol, and 2.22 g. (0.011 mol) of dicyclohexyl carbodiimide are stirred at 100 for 18 hours. After cooling the residue is chromatographed with hexane/ethyl acetate 99:1 on silica gel. A cis,trans mixture of 5-(7-isopropoxy 5 methyl-4-heptenyloxy)-1,3- benzodioxol is obtained. n ==l.5017.

Analysis: C H O (molecular weight: 306.4). Calc.: C, 70.6%; H, 8.6%. Found: C, 70.8%; H, 8.8%.

EXAMPLE 57 5- (5 -Isopropoxy-2-pentenyloxy l ,3-benzodioxol (according to process (c)) A mixture of 7.2 g. (0.05 mol) of 5-isopropoxy-2- penten-l-ol, 6.9 g. (0.05 mol) of 3,4-methylendioxyphenol, and 10.3 g. (0.05 mol) of dicyclohexyl-carbodiimide is stirred at 105 for 16 hours. After cooling 50 cc. of ether are added, the mixture is filtered and the filtrate is evaporated. The residue is chromatographed on silica gel with hexane/ethyl acetate 9:1 and 5-(5-isopropoxy-2-pentenyloxy)-1,3-benzodioxol is obtained as colourless oil which is identical with the product produced in accordance with Example 39.

EXAMPLE 58 4- (5 -Isopropoxy-2-pentenylthio -methyl] -chlorobenzol (according to process (d)) A solution of 8.0 g. (0.05 mol) of 5-isopropoxy-2- penten-l-thiol and 2 g. (0.05 mol) of sodium hydroxide in 30 cc. of ethanol are added dropwise' at 50 during the course of 45 minutes to a solution of 8.05 g. (0.05 mol) of p-chloro-benzylchloride in 25 cc. of ethanol, the temperature not exceeding 55. After the addition is complete the mixture is heated to 60 during 10 minutes. The reaction mixture is filtered, the ethanol is distilled oil and the residue is chromatographed on silica gel with chloroform, whereby 4-[(5-isopropoxy-2-pentenylthio)- methyl]-chlorobenzol is obtained which is identical with the compound produced in accordance with Example 40.

EXAMPLE 59 5-[ (5 -Isopropoxy-3-methyl-2-pentenyloxy) -methyl] 1,3-benzodioxol (according to process (d)) 3.16 g. (0.02 mol) of 5-isopropoxy-3-methyl-2-penten- 1-01 are added at room temperature to a solution of 1.36 g. (0.02 mol) of sodium ethylate in 30 cc. of ethanol. The solvent is distilled 011 at reduced pressure and the residue which is dried well at room temperature is dissolved in 30 cc. of dimethylsulphoxide. 4.3 g. (0.02 mol) of 3,4-methylenedioxy-benzylbromide (produced according to P. Karrer et al., Helv. Chim. Acta, 6, 905 [1923]) which are dissolved in 20 cc. of dimethylsulphoxide are added dropwise at to this solution. The mixture is stirred at room temperature for 2 hours and subsequently at 60 for 18 hours.

The reaction mixture is poured on 200 cc. of water, is extracted with ether and the ether extract is washed with saturated salt solution. After the drying of the ether extract with sodium sulphate and distillation of the solvent the residue is chromatographed on silica gel with hexane/ethyl acetate 9:1. The resulting cis/trans isomeric mixture of -[(5-isopropoxy-3-methyl-2-pentenyloxy)-methyl]-1,3-benzodioxol is identical with the isomeric mixture produced in accordance with Example 41.

EXAMPLE 60 1,4-Bis l-benzo dioxol-S-yloxy) -2-methyl-2-butene 3.2 g. (0.02 mol) of sodium salt of 3,4-methyendioxyphenol are suspended in 60 cc. of 1,2-dimethoxyethane and cooled to 0-5.. 2.28 g. (0.01.rnol) o. 1,4-hromo- 2-methyl 2-butene, dissolved in 20 cc. of 1,2-dimethoxyethane are added while stirring. The mixture is stirred at 20-25 during the course of 20 hours and 50 during the course of 5 hours; it is'subsequentlyffiltered andthe filtrate is evaporated. The residue is taken up in ether, extracted with saturated salt solution, the etherphase is dried with sodium sulphate and evaporated. The obtained viscous oil is purified by chromatography on silica gel with hexane/ethyl acetate 5:1 and subsequently by crystallization from ethyl acetate/hexane. M.P. 73.;574f. 1

Analysis: C I-I 0 (molecular weight: 342.3). Calc.: C, 66.7%; H, 5.3%. Found: C, 66.7%;'H, 5..6,%.

In analogous manner as described in Example 60, but using sodium salt of 4-hydroxy-benzoic methyl ester in the place of the sodium salt of 3,4-methylendioxy-phenol, the following compound is produced: H

EXAMPLE '61 4,4'-(2-Methyl-2-buten-1,4-ylendioxy)-bis(benzoic methyl ester) 1,4-Bis (pip eronyloxy) -2-methyl-2-butene Analysis: C H O (molecular weight: 370.4), Calm: C, 68.1%; H, 6.0%. Found; C, 68.0%;H, 6.5%. p

The alcohols of general formulaVHI required for the production of the compounds of formula I without isolation of the compounds of general formula II may be produced with the following Example:

EXAMPLE 63' q 5Isopropoxy-3-methyl-1 penten-3-ol 12 g. (0.5 mol) of magnesium'cuttingsare covered with a layer of 60 cc. of absolute tetrahydrofurane in an atmosphere of nitrogen in a flask equipped with a stirrer and a reflux condenser cooled with ice, andare heated to 40-45. 5 cc. of a solution of 53.5 g. (0.5 mol) of vinyl bromide in cc. of absolute tetrahydrofurane are added dropwise by means of a dropping funnel, whereupon an exothermic reaction sets in. The remaining vinyl-bromide solution is added dropwise at such afratethat the reaction mixture maintains a temperature of 4 516 50 (approximately 1 to 1% hours). Then the 'mix-ture -is stirred at 50 for 1 hour and 1 subsequentlycoole'd 'to 0, 52 g. (0.4 mol) of 4 isopropoxy-2 butanone in 100 cc. of absolute tetrahydrofurane are addeddropwise 'duiing the course of 45 minutes and while stir ring vigorously; the reaction mixture is subsequently stirred at room temperature during the course of 16hours. After this period 250 cc. of a 20% ammonium chloride solution are added during the course of 15 minutes to the reaction mixture which is cooled to 5-10. The mixture is stirred for15 minutes and extracted with ether. The ether extract is washed with water in a separatory funnel, is dried with sodium sulphate and evaporated. The residue is fractionated at 13 mm. pressure, whereby the 5-isopropoxy- 3-methyl-1-penten-3-ol distils at 7273. n 5: 1.4297.

Analysis: C I-1 0 (molecular weight 158.2). Calc;; C, 68.3%; H, 11.5%. Found: C, 68.1%; H, 11.4%.

Analysis percent, a Molee calcJfound Exnm- Empirical ular Starting compound of ple g formula weight B.P./mm. my C H S formula IX 64..."; 3-ethyl-5-isopropoxy-1-penten-3-ol CmHzuOg 172.3 8184/12 1.4346 1-isopropoxy-3-pentanone.

65...")..- 5-sc.hutoxy-3-methy1-1-penten-3-ol 010E200: 172.3 87-91/15 1.4352 4-sec.butoxy-2-butanone.

66 3-ethyl-5-see.butoxy-l-penten-B-ol. 11220 186.3 11315/30 1. 4380 l-sec.butoxy-B-pentanone.

67---... -tert.butoxy-3-methyl-1-penten-3-ol. CmHzuOz 172.3 78-81/12 1.4316 4-tert.butoxy-2-butanone.

68 5-isopropylthio-3-methyl-1penten-3 ol OBHMOS 174.3 7980/1.2 1.4813 4-isopropylth1o-2-butanone.

69 --5-sec.butylthio-3-methyl-1-penten-3-ol CioHruOS 188.3 8689/0.85 1.4844 18.; 2 4-sec.butylthio-2-butanone.

70 5-cyclohexyloxy-3-methyl-l-penten-3-ol 011E110: 198.3 87-90/0.6 1.4669 4-cyclohexyloxy-2-butanone.

71 5-cyclopentyloxy-Zi-methyl-l-penten-liol 011E200: 184.3 7679/1.2 1.4612 71.7 10.9 4-cyclopentyloxy-2- 71.6 11.0 butanone.

72 3-methyl-5-(Z-pentyloxy)-1-penten-3-ol 011E220: 186.3 6467/1.0 1.4358 4-(2-pentyloxy)-2-butanone 73 3-methy1-5-(3-pentyloxy)-1-penten-3-ol 011E 186.3 66-69/1.0 1. 4377 4-(3-pentyloxy)-2-butanone.

74; 5:11.butoxy-S-fiiethyl-1-penten-3-01 CwHzoOg 172.3 115l9/33 1. 4370 4-n.butoxy-2-butanone.

75 5-ethoxy-3-methyl-1-penten-3-ol 011E100; 144.2 90-92/46 1.4325 4-ethoxy-2-butanone.

7e 5-ethoxy-3.5-dimethyl-1-hexen-3-o1 01.11.00. 172.3 s7-s9"/1e 1.4383 69.7 11.7 4-ethoxy-4-methyl-2- 69.3 11.6 pentanone.

77 3-methyl-5-(6-methy1-5-hepten-2-yloxy)-1- 014112 0; 226.4 1.4627 74.3 11.6 4-(6-methyl-5-hepten-2- penten-S-ol. 74. 0 11. 6 yloxy)-2-butanone.

Produced in accordance with A. Hoffman, J. Amer. Chem. Soc. 49, 532 [1927];

The compounds of general formula II may be produced in accordance with the following Example:

. EXAMPLE 78 6-Ethoxy-1-bromo-3-methyl-2-hexene 3.9 g. (0.03 mol) of S-ethoxy-Z-pentanone (produced in accordance with A. H. Tracy et al., J. Org. Chem., 6, 68 [1941]) in 10 cc. of tetrahydrofurane are added dropwise at 0 during the course of 30 minutes and while stirring to the Grignard reagent, produced from 0.96 g. (0.04 mol) of magnesium and 4.3 g. (0.04 mol) of vinyl bromide in cc. of tetrahydrofurane. After stirring at 20-25" for 15 hours the mixture is cooled to 5-10"; cc. 01 20% ammonium chloride solution are added and after 10 minutes'it is extracted with ether. The ether extract is washedwith saturated salt solution, dried with sodium sulphate and evaporated. The residue which is uniform in accordance with gas-chromatography (4.5 g. of 6-ethoxy-3-methyl-1-hexen-3-ol) is added at 0 during the course of 5 minutes to 12 cc. of 48% hydrobromic acid. The mixture is stirred at 05 during the course of minutes and then the ether is extracted, the ether solution is washed with saturated salt solution, dried with sodium sulphate and evaporated. The resulting 6-ethoxy- 1-bromo 3-methyl-2-hexene is used without purification.

EXAMPLE 79 1-Bromo-4-isobutoxy-2-methyI-Z-butene 6.8 g. (0.03 mol) of 1,4-dibromo-2-methyl-2-butene are dissolved in 15 cc. of isobutanol and 2.9 g. (0.03 mol) of sodium isobutylate in 50 cc. of isobutanol are added at 0. After stirring at 0 for 2 hours the mixture is stirred at 20-25 for 16 hours. The mixture is filtered and the filtrate is evaporated at reduced pressure. The residue is dissolved in ether, washed with saturated salt solution and dried with sodium sulphate. The ether is evaporated and the residue is distilled at 13 mm. The product has a B.P. of 128138/13 mm.

Analysis: C I-I BIO (molecular weight: 221.1). Calc.: C, 48.9%; H, 7.7%; Br, 36.1%. Found: C, 49.0%; H, 7.8%; Br, 35.6%.

The compounds of general formula II via formula XIV may be produced in accordance with the following Example:

EXAMPLE 1-Bromo-6-isopropoxy-4-methyl-3-hexene A solution of 46 g. (0.35 mol) of 4-isopropoxy-2- butanone in 100 cc. of absolute tetrahydrofurane is added dropwise at 5 during the course of 10 minutes in an atmosphere of nitrogen and while stirring to the Grignard reagent (according to E. Renk et al., J. Amer. Chem. Soc., 83, 1987 [1961]) produced from 9.06 g. (0.38 mol) of magnesium and 42.8 g. (0.35 mol) of cyclopropyl bromide in 460 cc. of absolute tetrahydrofurane. After strirring the reaction mixture at room temperature for 20 hours saturated ammonium chloride solution and ice are added and the mxiture is extracted with ether. The ether extract is washed with saturated salt solution, dride over sodium sulphate and evaporated. The resulting 2-cyclopropyl-4- isopropoxy-Z-butanol, having a B.P. of 75-77 12 mm., may be worked up without purification.

19 cc. of 48% hydrobromic acid are added dropwise at 0 during the course of 15 minutes and while stirring to 27.7 g. of crude product. The mixture is stirred at 0-5 during the course of 30 minutes and subsequently extracted with ether. The ether extract is washed with water, saturated sodium bicarbonate, and saturated salt solution, dried over sodium sulphate and evaporated. The residue (20.2 g.) is chromatographed with hexane/ethyl acetate 98:2 and :5 on 1 kg. of silica gel. A chromatographically uniform cis/trans isomeric mixture of 1bromo-6-isopropoxy-4-methyl-3-hexene is thus obtained. r1 1.4721.

Analysis: C H BrO (molecular weight: 235.2). Calc.: C, 51.1%; H, 8.1%; Br, 34.0%; 0, 6.8%. Found: C, 50.8%; H, 8.0%; Br, 34.2%; 0, 7.0%.

EXAMPLE 81 4-Isopropoxy-2-butanone 0.3 g. of concentrated sulphuric acid are added to 7.2

g. (0.12 mol) of isopropanol. A mixture of 21 g. (0.3

mol) of vinyl methyl ketone and 36 g. 0.6 mol) of isopropanol is added dropwise at room temperature during the course of 1 hour and while stirring, the temperature EXAMPLE 82 4- 6-Methyl-S-hepten-Z-yloxy) -2-butanone B.P. 82-85 1.0 mm.

Analysis: C H O (molecular weight: 198.3). Calc.: C, 72.7%; H, 11.2%. Found: C, 71.8%; H, 11.1%.

The compounds of general formula 11, wherein Y signifies oxygen and Hal signifies chlorine, may, for example, be produced as follows:

EXAMPLE 83 1-Chloro-5-isopropoxy-3-methyl-2-pentene 32.4 g. of chloromethyl-isopropylether are added dropwise at during the course of 40 minutes and while stirring to 20.4 g. (0.3 mol) of isoprene and 0.3 g. of zinc chloride. The mixture is then stirred at room temperature for 24 hours. The reaction mixture is taken up in ether, is washed with water and subsequently with sodium bicarbonate solution and again with water. The ether phase is dried with sodium sulphate, the ether is distilled off and the residue is distilled at 12 mm., whereby 1- chloro--isopropoxy-3-methyl-2-pentene is obtained as colourless oil. B.P. 8692 12 mm., n Q=1.4553.

Analysis: C H CIO (molecular weight: 176.7). Calc.: C, 61.2%; H, 9.7%; CI, 20.1%. Found: C, 61.3%; H, 9.6%; Cl, 20.3%.

EXAMPLE 84 1 1-Chloro-S-isopropoxy-Z-pentene 13 g. (0.24 mol) of butadiene are introduced at l015 during the course of 1% hours and while stirring into a suspension of 0.8 g. of newly melted zinc chloride in 21.7 g. (0.2 mol) of chloromethyl-isopropylether. The mixture which has now turned yellow is stirred at for 1 hour. After this period 20 cc. of 10% sodium car- 'bonate solution are added dropwise, 100 cc. of benzene are added and the aqueous phase is separated in a separatory funnel. The benzene solution is washed with 10% sodium carbonate solution and subsequently with water, is" dried with magnesium sulphate and evaporated at reduced pressure. The residue is distilled at 90 mm. B.P.

' of '1-chloro-5-isopropoxy-Z-pentenez 110-112/ 90 mm.

Analysis: C H ClO (molecular weight: 162.7).,Calc.: C, 59.1%; H, 9.3%; Cl, 21.8%. Found: C, 59.2%; H, 9.3%; CI, 21.1%. I

. 22 The compounds of general formula IV may be produced in accordance with the following Example:

EXAMPLE 5-(4-Bromo-3-methyl-2-butenyloxy)-1,3-benzodioxol 25.1 g. (0.11 mol) of 1,4-dibromo-2-methyl-2-butene are dissolved in cc. of 1,2-dimethoxyethane and cooled to -20". 16.0 g.. (0.1 mol) of sodium salt of the ..3,4- methylenedioxy-phenol in cc. of 1,2-dimethoxyethafie are added during the course of 15 minutes to this solution. After stirring at 0 for 1 hour'and at 20 for 15 minutes the solvent is distilled off in a vacuum. The residue is dissolved in ether, is washed with saturated salt solution and dried with sodium sulphate. The ether is evaporated and an oily residue remains which is purifiedby chromatography on silica gel with hexane/ethyl acetate 9:1.

Analysis: C H BrO (molecular weight: 285.1). Calc.: C, 50.5%; H, 4.6%; Br, 28.0%; 0, 16.8%. Found: C, 50.4%; H, 4.5%; Br, 28.3%; 0, 17.0%.

In analogous manner as described in Example 85, but using the sodium salt of p-hydroxy-acetophenone in the place of the sodium salt of 3,4-methylendioxy-phenol, the following compound of general formula IV is produced:

EXAMPLE 86 4'-(4-Bromo-3-methyl-2-butenyloxy) -acetophenone Analysis: C H BrO (molecular Weight: 283.2). Calc.: C, 55.1%; H, 5.3%; Br, 28.2%. Found: C, 54.7%; H, 5.3%; Br, 28.5%.

In analogous manner as described in Example 85, but using the sodium salt of the 4-hydroxy-benzoic methyl ester in the place of the sodium salt of 3,4-methylendioxyphenol, the following compound is produced.

EMMPLE 87 4- (4-Bromo-3-methyl-2-butenyloxy)-benzoic methyl ester Analysis: C H Br O (molecular Weight: 299.2). Calc.: C, 52.2%; H, 5.1%; Br, 26.7%. Found: C, 52.3%; H, 5.1%; Br, 26.4%.

EXAMPLE 88 5-[(4-Bromo-3-methyl-2-butenyloxy)-methyl]- 1,3-benzodioxol 8.7 g. (0.05 mol) of sodium salt of the 3,4-methylendioxybenzylalcohol are added at 0 during the course of 15 minutes and while stirring to 12.5 g. (0.055 mol) of 1,4-dibromo-2-methyl-2-butene which is dissolved in 100 cc. of 1,2-dimethoxyethane. The mixture is stirred at 2025 for 16 hours and at 50 for 15 minutes. The solvent is then distilled off at reduced pressure and 100 cc. amounts of water and ether are added to the residue. The aqueous phase is separatedin a separatory funnel, the ether phase is extracted with saturated salt solution, is dried and sodium sulphate and evaporated. The residue is chromatographed on silica gel with hexane/ethyl acetate 9:1, whereby the 5-[(4-bromo-3-methyl-2butenyloxy)- methyl]-1,3-benzodioxol is obtained as uniform colourless oil.

Analysis: C H 5BrO (molecular weight: 299.2). Calc.: C, 52.2%; H, 5.1%; Br, 26.7%. Found: C, 51.8%; H, 5.0%; Br, 27.6%.

EXAMPLE 89 5- (4-Bromo-2-butenyloxy) -1,3-b enz"odioxol 6.4g. (0.04 mol) of sodium salt of 3,4-methylendioxyphenol are added at 20 to a solution of'8L6 g. (0.04 mol) of 1,4-dibr'omo-2-butene in 100 cc. of 1,2-dimethoxyethane. The mixture is stirred at 0 for 3 hours and subsequently at room temperature for 1 hour. The'solve'nt is distilled off at reduced-pressure and the residue is taken up in ether. Theether solution is extracted with saturated salt solution, is dried with sodium sulphate and evaporated.

' yellow oil.

The residue is purified by ,chromatography on silica gel With hexane/ethylacetate 95.1. The (4,-bromo-2-butenyloxy)- 1,3-benzodioxo1 is obtained as colourless oil.

Analysis: C H BrO (molecular weight: 271.1). Calc.:;C, 48.1%; H, 4. l.%;,Br, 29.5%. Found:-.- C, 48.6%

In analogous manner 'as described in Example 89 but using the sodium salt 'ofp-hydroxyacetophenone;-inthe place" of the sodiuniisalt "of 3,4 nlethylendioxy phenol, l the following cdmpound'is producedz' f ffi; 1 QEXAMPILE 9,0

1 4'-(4-Bromo 2-biitenyloxy) abetophenone jAnalysis C I-l gBro (molecular weight: 269.1). Calc.:

EXAMPLE91IQ 1 I 5-['(4-Bromo 2 butenyloxy)-1nethyl]-1,3-benzodioxol and the ether is then: distilled off and the residue is chromatogra'phed on silica gel with hexane/ethyl acetate 9:1.

The chromatographically uniform 5-[(4-bromo-2-butenyloxy).-methyl] 1,3 benzodioxol is'obtained as slightly Analysis:. C12H13B1O3 (molecular weight: 285.1).

Calc.: c, 50.5%; H, 4.6%; Br, 28.0%. Found: 0, 50.4%;

H, 4.7%; Br, 27.5%.

The compounds of general formula VI may be produced inaccordance with the following Example:

EXAMPLE 92 7-Isopropoxy-5 methyl-4-heptenol A solution of 3.68 g. (0.02 mol) of -7-isopropoxy-5- methyl-4-cis,trans-heptenal in 6.5 cc. of ethanol is added dropwise at 05 during the course of 10 minutes and whilesti'rring to a mixtureof 0.76 g. "(0.02 mol) of sodium borohydride, 40 cc! of water, 4 drops of 2N sodium hydroxide, and 40 cc. of ethanol. After stirring for 2 hours at room ftemperature 60 cc. of water are added to the reaction mixture which is concentratedby evaporation in a vacuum and extracted with ether after saturation with common salt. The ether extr'act'is washed with water and saturated salt"solution, dried over sodium sulphate and 1 evaporated. The residue is chromatographed with hexane/ "ethyl acetate 9:1 on 180 gi of silica gel, whereby pure 7- isopropoxy-5-methyl-4-cis,trans-heptenol is obtained. Analysis: C H O (molecular Weight: 186.3). Calc.: C, 70.9%; H, 11.9%;Found: C,70.9%; H, 11.9%.

The compoundsof'general formula XVI are produced inactiordance the; following Example:

EXAMPLE 93 7-Isopropoxy-5-methyl-4-heptenal i 15.8 g. (0.1 mol) of 5-isopropoxy-3-methyl-1-penten-3- 01: (produced in accordance WithExar'nple 63) and 20.0

g. of mercury acetate are kept "in 180 cc. of ethylvinyl Whisk?! P ldQ ttPtPid- :50. Pwf- .5.% P t i m-s bonate solution are added; after 3 hours and .the 'mixture is, extracted with hexane. The hexane extract is evaporated I a 5 i n residue is. heated to 165 168 .-,during v1 /z hoursin v sopropoxy-S methylA-heptenal; 7073/ 9.8 rlD ";1.447,6.-

8.13 g. (0.05 mol) of 1-chloro-5-isopropoxy-2-pentene are added to a solution of "6.5" g. ;of'sodi1im carbonate in cc. of water and the mixture is heated to -98 during 13 hours'f Af-ter cooling-the organieparts are extracted with benzene, the "beiizene'extract isf'waslied wilth saturated "salt solution and dried with sodium sulphatefiThe 'solvent is distilled "ofi' 'a'nd then" it "is distilled atfl reduced pressure. According w gas chromatog'raphy pure 5-isopr'opoxy-2- penten-l-ol distils at 102104/ 15 mm. n =1.4363.

Analysis: C H O (molecular weight: 144.2). Calc.: C, 66.6%; H, 11.2%; 0, 22.2%. Found: C, 66.4%; H,

In analogous manner as described in Example 94=the following compound is produced.

I EXAMPLE 95 5-Isopropoxy-3-methyl-2-penten-l-ol B.P. 1151l8/15 mm.

Analysis: C H O (molecular weight: 158.2). Calc.: C, 68.3%; H, 11.5%; 0, 20.2%. Found: C, 67.2%; H, 11.3%;0, 19.3%. v 1

EXAMPLE 96 5-Isopropoxy-2-pentenl-thiol A mixture of 8.1 g. (0.05 mol) of 1-chloro-5-isopropoxy- Z-pentene, 328 g. (0.05 mol) of thiourea, and 5 cc. of water are heated to 98 during the course of 35 minutes and stirred at this temperature for 30 minutes. The homogeneous reaction mixture is cooled to 60 and 10 cc. (0.05 mol) of 5N caustic soda solution are added dropwise at this temperature. The mixture which again has rendered heterogeneous is heated to 100 with stirring, is cooled after 5 minutes and poured on water. The reaction mixture is extracted with ether, the ether extract is washed with saturated salt solution, is dried with sodium sulphate and the ether is evaporated. The residue is fractionated at 16 mm., whereby the 5-isopropoxy-2-penten-l-thiol is obtained as malodorous oil which is uniform according to gas-chromatography; it has a B.P. of 87-89/16 mm.

7 7) :-X I O stituted bylower acyloxy; and wherein, I I v.ZI is alkyl of 1 to 5 carbon atoms,.alkenyl of 2to ,12 Q ,carbonatoms, alkoxy of 1 to 5 carbon atoms, alkenyloxy of 2 to 12 carbon .atoms'formyl, alky'l' carbonyl h '1. f. 1 fiarbqn'a ,a k 'x'y rbony f..2,to"i6 'cairbon atorni n ionoor di alk'yl'subs ti ted j'carbamoyl'ea chj'alkyljsubstituent ofwhicli is I to 5 egalbon atoms, alkoxyjrn'ethylene of 2 to 6 carbon atoms, alkylthio of 1 to 5 carbon atoms," fluorine, chlorine,

I bromine, cyano or nitro, I H R and'R which may bethe same or diifereiit, are

i Bach y n or alkyl' on to 5 carbon atoms,

qisOorl,

represents a single R is alkyl of 1 to 11 carbon atoms or an acyclic hydrocarbon of up to 11 carbon atoms having one or two double bonds or one triple bond,

R R R R R R R and R which may be the same or different, are each hydrogen, alkyl of 1 to 5 carbon atoms or alkenyl of 2 to 6 carbon atoms,

Y is oxygen or sulphur,

X is oxygen, sulphur, -OCH or SCH s, v and w, which may be the same or different, are

each or 1, and

z is 1, 2 or 3.

2. The compound of Claim 1, which is -(3-ethyl-5- sec.-butoxy-2-pentenyloxy)-1,3-benzodioxol.

3. The compound of Claim 1, which is 5-(3-ethyl-5-isopropoxy-Z-pentenyloxy)-l,3-benzodioxol.

4. The compound of Claim 1, which is 5-(5-tert.butoxy- 3-methyl-2-p entenyloxy) -1, 3 benzodioxol.

5. The compound of Claim 1, which is 5(5-isopropylthio-3 methyl-Z-pentenyloxy) -1,3 b enzodioxol.

6. The compound of Claim 1, which is 5-[3-methyl-5- (3 pentyloxy) 2-pentenyloxy] -1,3-benzodioxol.

7. The compound of Claim 1, which is 5-[3-methyl-5- (2-pentyloxy 2-pentenyloxy] 1,3 benzodioxol.

8. The compound of Claim 1, which is 5-[(5-isopropoxy-3methyl-Z-pentenyloxy)methyl]-1,3-benzodioxol.

9. The compound of Claim 1, which is 5-(5-isopropoxy- 3-methyl-2-pentenyloxy)-1,3-benzodioxol.

10. The compound of Claim 1, which is 5-(5-ethoxy-3- methyl-2-pentenyloxy)-1,3-benzodioxol.

11. The compound of Claim 1, which is 5-(5-n.butoxy- 3-methyl-2-pentenyloxy)-1,3-benzodioxol.

12. The compound of Claim 1, which is 5-(6-ethoxy-3- methyl-Z-hexeneyloxy) -1,3-benzodioxol.

13. The compound of Claim 1, which is 5-(4-isobutoxy- 2-methyl-2-butenyloxy)-1,3-benzodioxol.

14. The compound of Claim 1, which is 5-(6-isopropoxy-4-methyl-3hexenyloxy)-l,3-benzodioxol.

15. The compound of Claim 1, which is 5-(S-isoproproxy-Z-pentenyloxy 1,3 b enzodioxol.

16. The compound of Claim 1, which is 5(4-isobutoxy- 3-methyl-2-butenyloxy -1,3-benzodioxol.

17. The compound of Claim 1, which is 5-(4-n.butoxy- 3-methyl-2-butenyloxy)-l,3-benzodioxol.

18. The compound of Claim 1, which is 5-[(4 isobutoxy-3methyl-Z-butenyloxy)mcthyl]-1,3-benzodioxol.

19. The compound of Claim 1, which is 5-(4-isobutylthio-3-methyl2-butenyloxy)-1,3-benzodioxol.

20. The compound of Claim 1, which is 5-(4-isobutoxy- 2-butenyloxy)-1,3-benzodioxol.

21. The compound of Claim 1, which is 5-[(4 isobutoxy-2-butenyloxy)methyl]-1,3-benzodioxol.

22. The compound of Claim 1, which is 5-(7 isopropoxy-5-methyl-4-heptenyloxy)-1,3-benzodioxol.

23. The compound of Claim 1, which is 5-[3-methyl-5- (6-methyl-5-hepten-2-yloxy)2-pentenyloxy] 1,3 benzodioxol.

24. The compound of Claim 1, which is 5-[(5-ethoxy- 3 5 dimethyl-Z-hexeneyloxy) methyl] 1 3 benzodioxol.

References Cited UNITED STATES PATENTS 3,709,914 1/ 1973 Siddall 260-3405 3,709,915 1/ 1973 Siddall 260-340.5

FOREIGN PATENTS 2,103,733 4/ 1972 France.

1,144,906 3/ 1969 Great Britain.

OTHER REFERENCES Ellis et al.: PANS, vol. 16, No. 3, 1970, pp. 434-46. Chang et al.: Agr. Biol. Chem, vol. 35, No. 8, pp. 1307-9.

DONALD G. DAUS, Primary Examiner I. H. TURNIPSEED, Assistant Examiner US. Cl. X.R. 260340.3, 473 R, 592, 609 R, 611 A; 424-282 

